Phenolic condensation product and method of preparing same.



UNITED STATES PATENT ()FFICE.

JONAS W. A'YLSWORTH, OF EAST ORANGE, NEW JERSEY, ASSIGNOR OF ONE-HALF TOFRANK L. DYER, F MONTCLAIR, NEW JERSEY.

PHENOLIC CONDENSATION PRODUCT AND METHOD OF PREPARING SAME.

No Drawing.

To all whom it may concern Be it known that I, JONAS IV. AYLswoRTH, acitizen of the United States, and a resident of East Orange, in thecount-y of Essex and State of New Jersey, have made a certain new anduseful Invention in Phenolic Condensation Products and Methods ofPrep'ar-- ing Same, of which the following is a description.

My invention relates to infusible condensation products of phenol andsubstances containing the methylene radical and met-hods for preparingthe same, and my object is to produce a composition of this class havingvarious novel and useful characteristics, and to devise a method forpreparing the same, all as will be hereinafter more particularlydescribed in the following specification and pointed out in the appendedclaims.

In my application Serial No. 196,060, composition and process formanufacturing the same, filed May 14, 1909, I describe an ultimateinfusible insoluble condensation prodnot of phenol and formaldehyde ortheir equivalents, which is prepared by first forming a fusiblecondensation product of phenol and formaldehyde, in which the aldehydeis all combined with the phenol, andthe ph enol is all, or nearly all,combined with the aldehyde, vand then causing a further reaction betweenthe same andan additional amount of an aldehyde, preferably a polym- 5erized form of formaldehyde, and in an 3 the fusible condensationproduct and any free phenol contained therein, to form the 1 desiredultimate infusible condensation product. Or a final product having'manyof the advantages of the above described product might be obtained, asdescribed in the said application, by combining the polymerizedformaldehyde with various of the phenol resins, or so-called shellacsubstitutes on the market.

In my present application, I will describe a product formed by combininga fusible anhydrous resinous condensation product of a phenol and analdehyde with a methyleneamin compound, such as hexa-methyleneamin, orhexa-methylene-tetra-amin as it is .-s01netimes called (CH N,. Or inplace of the latter, the mixture of salts obtained by the combination ofaqueous solutions of ammonia and formaldehyde might be used.

Specification of Letters Patent.

Application filed February 11, 1910.

amount just sufficient to combine with all of Patented Mar. 19, 1912.

Serial No. 543,238.

The fusible anhydrous resinous condensation product referred to above(hereinafter termed a phenol resin) is first prepared by "causing areaction between suitable amounts of phenol and formaldehyde or theirequivalents without the aid of any catalytic or condensing agent, asdescribed in my application above referred to. This operation isconducted in such a manner that a fusible anhydrous resin results, whichis thinly fluid when molten, the resin being completely dehydrated,after the condensation reaction, by heating to a suflicient temperature,as, 400 F. This isamixed with a methylene-amin compound, also anhydrous,in definite proportions, forming a mass which is fluid at temperaturesbetween 200 degrees F and 240 degrees F., and which, when maintained atthese temperatures or higher temperatures for a short time, will hardento a hard infusible chemically inert mass. This ultimate condensationproduct possesses great tensile strength. Counteracting pressure neednot be used during the reaction between the fusible condensation productand the methylene-amin compound, and this reaction is not accompanied byevolution of formaldehyde, water, or other gaseous products, which, ifevolved, would bubble through the mass and render the product porous anduseless for many purposes. v t

VVher-ever in the specification, I refer to a methylene amin compound, Irefer to hexamethylene-tetra-amin orjthe mixture of salts' which, asstated, may be obtained by the combination of aqueous solutions'ofammonia and formaldehyde which consists of hexa-methylene tetra aminapparently in many instances admixed with other methylene-amins or thechemical equivalents of such substances.

It will be seen that the process thus far disclosed differs from theprocess for forming an infusible phenolic condensation product--disclosed in my application above referred to, broadly by thesubstitution of a methylene-amin compound for the paraformaldehyde orother polymerised formaldehyde, which, in my previous invention, Icombine with the fusible phenol resin to form the ultimate condensationproduct. I have found that the methylene-amin is superior to an aldehydefor addition to the phenol resin for hardening the mass, for a number ofreasons. It has no tendency to cause foaming of the mass even if anexcess of methylene-amin is used above the amount which I havediscovered to be necessary to combine with all of the phenol resin toharden the same. Paraformaldehyde or other aldehyde added to the phenolresin in my previous invention tends to escape as gas if an excess isused above the amount necessary to combine all of the phenol resin, orif the final reaction is carried on too speedily or under too intense aheat. In the case of the amin compound, however, there is no freeformaldehyde and the methylene radical can only be separated from thenitrogen by its being taken away from the same by reaction with thephenol resin with which it combines in exchange for some of the hydrogenof the resin which unites with the nitrogen, to form ammonia. Methylenenever exists in the free state, and hence the methylene-amin used cannotcause bubbling or gassing. Therefore, when the methyleneimaldehyde arecaused to combine with three amin is used, great care need not be takento prevent the'addition of a slight excess of this element to preventfoamingof the mass. It will be seen that my invention involves broadlythe hardening of a fusible phenolic condensation product into aninfusible product by the addition to and reaction with the fusibleproduct of a substance containing the methylene radical, other than theoxid or hydroxid of methylene, which substance is not evolved as gasduring its addition to the fusible condensation product, from which themethylene radical is taken only by combination thereof with the phenolresin, and which does not evolve steam or other gaseous products underheat treatment. The methylene-amin derivatives and polymers, such asthose to which I have referred, possess these characteristics. Anotheradvantage of the methylene-amin compound over the paraformaldehyde forthe functionreferred to is that it will cause a hardening of the mass ata much lower j 'weight here shown when prepared with pure ;ingredientsand at proper temperatures. practical operations, however, such care asfto purity and temperature is not essential to obtain a product suitablefor the use herein mentioned, and such phenol resin products may be amixture of the above compositions with others of higher molecular weightdue fto polymerization or to decomposition from temperature than willthe paraformaldehyde. This is of particular advantage when the substanceis to be used in mixture with or in impregnating cellulose fabrics, woodpulp, or other substances which are injured by temperatures above 280degrees F.

A further distinction. should be noted of my improved product andprocess here described and claimed, as well as that described andclaimed in my earlier application above referred to over the prior art,in that no free or'combined water remains in the final product, whichresult always takes place when the so-called intermediate or partialcondensation product is hardened by heating under a counteractingpressure greater than the vapor pressure of the contained water of suchintermediate product. The intermediate or partial condensation hardensand becomes infusible.

parts of phenol by molecular weight. molecules of formaldehydeapparently com- .bine with three molecules of phenol in the fmannerindicated with the evolution of two fmolecules of water. in the case ofthe fusible condensation prodfuct described and claimed in myapplication i above referred to, the proportions there given, as of 650parts of a 4.0 per cent. solution by volume of formaldehyde to 1000Eparts of phenol, being such as to give the Emclecular proportion of-twoparts of for-; maldehyde to three parts of phenol, here stated, afterthe escape of a slight excess of Qforma'ldehyde above the molecularpropor- ;tion-, which is lost during the operation. @Thisformula gives amolecular weight for Qthe fusible product of 306 which checks up' ;quitewell with the determination of the weight made 'by'physical means,indicating :that the moleculecannot be of double 1noparently, the oxygenatom maldehyde molecule takes one hydrogen vatom from each phenolmolecule on each drate it will transform it into a final infusibleproduct.

By quantative synthesis, I have determined the apparent constitution ofthe particular phenol resin which has the desirable properties requiredfor a mass which will be sufliciently fluid when molten to be cast at atemperature below that at which the mass This phenol resin or fusiblecondensation product of phenol and formaldehyde is apparently That is,approximately two parts of for- Two This is equally true lecular weightor any other multiple of the long treating at high tem erature. Apromeach forside of it, as indicated in the diagram, to form water.

To produce the final product, I combine 100 parts by weight of thefusible anhydrous pure phenol resin with from 7.6 to 12 parts ofhexa-methylene-tetra-amin at a temperature of preferably 220 degrees F.The proportions require to be varied within the limits indicated,because the fusible resin sometimes contains more or less free phenol,which should be combined with the methylenc radical of themethylene-amin to produce the final infusible product. This is inagreement with the following equation:

This forms the same final product as that disclosed and claimed in myabove mentioned application, except that in the case of the latter, sixmolecules of water are evolved in place of the four molecules of ammoniain the equation given above. This reaction causes the formation of aninfusible refractory resinous amorphous mass of pale yellowish ambercolor when reacting substances are pure. The ammonia radical, NH isretained in the mass in unstable combination and part may be removed bypulverizing and warming. Half of the ammonia is liberated from theproduct at about 260 degrees F. if it is formed in thin films tofacilitate the removal of the ammonia, and at 840 degrees F. practicallyall of the ammonia is evolved. It is, however, not practicable to sotreat all objects to remove the ammonia by simple heat treatment, andeven when such heat treatment is resorted to, the result is not thecomplete elimination of the ammonia, and considerable internal stressesmay be set up which are likely to cause cracks and warping in theproduct. If ammonia is not removedit remains either imprisoned in theinter-molecular spaces of the mass, or in loose combination therewith.This product maycause corrosion of certain metals when it is used incontact with them, and on account of its tendency to absorb traces ofwater, the otherwise excellent insulating qualities of the product areimpaired. To overcome these objectionable features, I prefer to add tothe mass before hardening, a substance which will combine with and fixthe ammonia and render it a permanent harmless constituent of theproduct. The substances which I find as a class to be satisfactory forthis purpose are the organic acid anhydrids. Those which I findparticularly well suited for the purpose are the anhydrids of the highermembers of the series C H O or the acetic series, as it is often called,and also benzoic and phthalic anhydrid. The action of any of thesesubstances is to combine withithe ammonia and form acid amids, whichremain in the product as a solid solvent of the same.

The anhydrids of the organic acids are effective when used in amountsnecessary to fix all or part of the ammonia in the product. For mostpurposes, one-half the amount necessary to combine with the ammonia issufficient, as a part of the ammonia is retained so tenaciously withinthe sub 7 stance as to be unobjectionable. If any traces, of moistureare present in the ingre-. clients, they are effectively fixed by theacid, anhydrid. It should also be noted that if any free phenol ispresent in the fusible resin to which the methylene-21min compound andthe acid anhydrid are added, it

may be combined with the acid anhydrid to form a phenyl ester. Ifbenzoic anhydrid is used, the proportion should be about phenol resin100 parts, hexa-methylene-tetraamin 7.6 to 12 parts, benzoi'c anhydrid 4to 9 parts. If stea-ric anhydrid is used, the

proportion should be about phenol resin 100 parts,hexa-methylene-tetra-amin 7.6 to 12 parts, stearic anhydrid 9 to 15parts. The

proportions vary slightly if other of the ammonia fixing agentsmentioned are used, as

may be determined by experiment. The

amount of whatever anhydrid is used depends more or less upon themolecular weight of the particular anhydrid used. If

the stearic anhydrid is used, it should be noted that this substancedoes not perfectly dissolve in the amount of phenol resin required, so,therefore, it is advisable to add a small amount of a substance whichwill cause the stearic anhydrid to emulsify or become miscible. The acidamid of stearic or other fatty acid is suitable when added in smallamounts.

It should be noted that when an organic acid anhydrid is added to themass it performs a triple function, namely, to fix the ammonia,'to fixany traces of moisture which may be present in the ingredients, and toact as a solid solvent for the final product. As I stated in thespecification of my previous application referred to, I define a finalproduct solvent as a substance which will dissolve the ultimatecondensation product or combine therewith at the baking temperature,render it plastic at such temperature and remain as a part of theproduct in the condition of solid solution when hot or cold. Any of thesolid solvents referred to in the above mentioned application may beused in place of the organic acid anhydrid when it is not deemednecessary to fix the ammonia in the composition. Thus, I may usenaphthalene and some of its derivatives such as nitro and chloroderivatives, especially the mono-nitro and di-nitro and mono-chloronaphthalenes, di-nitro-benzene, preferably the meta varietv, acetanilid,ricinoleic acid, ricinelaidic acid, and their anhydrids, anddi-phenylamin in suitable proportions, as described in my applicationabove referred to. It is obvious that the mass may have incorporatedtherewith any of the various fibrous or inert powdered substances asfillers, and also pigments as desired.

I do not limit the invention to the particular methylene-amin compoundspecifically referred to, the heXa-methylene-tetraamin being given forthe purpose of definite description, since it is a well known substance,which may readily be obtained in the pure state, other methylene-amins,such as the substance produced by the action of liquid ammonia onformaldehyde or its polymers in various proportions giving equally goodresults. If desired, an acid amid of one of the higher members of theacetic series of acids may be formed and added to the ingredients,instead of adding the corresponding acid anhydrid and forming the amidwithin the mass by reaction between the anhydrid and the containedammonia. My ultimate product is particularly useful when it contains asuitable acid amid, either formed by the interaction of the added acidanhydrid with the ammonia within the mass, or previously formed andadded as a separate ingredient, as described, because the amid acts as asolid solvent and renders the mass sufficiently plastic when heated totake an impression from a die or mold. This effect was described inconnec tion with the description of the functions of the product solventelements in my previous application above referred to. I may also use anexcess of the fusible phenol resin as a solid solvent if I desire. Inthat case, an amount of the methylene-amin less than the amountnecessary to combine with quite all of the fusible phenol resin would beadded to the latter, so that the uncombined phenol resin, of an amountabout equal to that of the other solid solvent elements referred to,would be provided for acting as a solid solvent for the final product.

. In the claims, the term phenol is to be understood as including thehomologues and other equivalents of phenol, such as cresol, and

the term formaldehyde is to be understood as including the polymers offormaldehyde.

In this application the products in which solid solvent elements areincluded, or in which ammonia has been-fixed by combination withsuitable ammonia fixing ingredients, and the processes for forming thesame, are not claimed, as the subject matter thereof has been dividedout from this application and appears in my divisional application, No.653,402, filed Oct. 7, 1911.

Having now described my invention, what I claim and desire to protect byLetters Pat- 'ent is as follows:

1. The process of forming a hard infusible insoluble final condensationproduct which consists in incorporating with a fusible phenoliccondensation product a condensation product of ammonia and formaldehydeor polymer thereof, and heating the mass sufficiently to cause theingredients-to combine and the mass accordingly to be transformed intosaid hard infusible insoluble product, substantially as described.

2. The process of forming a hard infusible insoluble final condensationproduct which consists in incorporating with a fusible phenoliccondensation product hexamethylene-tetra-a1nin of quantity at leastsufficient to combine with all of the fusible condensation products andany free phenol which may be associated therewith on application ofsuificient heat, and heating the mass sufficiently to cause theingredients to combine and the mass accordingly to be transformed intosaid hard infusible insoluble product, substantially as described.

3. The process of forming a hard infusible insoluble final condensationproduct which consists in forming a fusible phenolaldehyde condensationproduct having no free aldehyde, incorporating therewithhexamethylene-tetra-amin, and heating the mass to render the same hardinsoluble and infusible, substantially as described.

4-. The process of forming a hard infusible insoluble final condensationproduct which consists in forming a fusible anhydrous phenolaldehydecondensation product having no free aldehyde, incorporating therewithanhydrous heXamethylene-tetraamin, and heating the mass to render thesame hard. insoluble and infusible,.substantially as described,

5. The process of forming a hard condensation product whichconsists inincorporating a fusible phenolic condensation product with hexamethylene tetra. amin,

and heating the'same sufficiently. to harden the mass, substantially asdescribed.

6. The process of forming a hard condensation product which consists inincorporating a fusible anhydrous condensation product of a phenol andformaldehyde with heXa-methylene-tetra-amin, and heating the samesufliciently to harden the mass, substantially as described.

7 The process of forming a hard infusible condensation product whichconsists in incorporating a fusible anhydrous phenolic condensationproduct in thinly fluid condition with anhydrous hexamethylene-tetraaminin definite proportions, and heating the same sufficiently to form saidhard infusible product, substantially as described.

8. The process of forming a hard infusible condensation product whichconsists in incorporating a fusible anhydrous phenolic con densationproduct in thinly fluid condition with anhydrous heXamethylene-tetraaminindefinite proportions, and heating the same suiiiciently under pressureno greater than atmospheric to expelany water contained therein, andform said hard infusible mass, substantially as described.

9. The process of forming a hard infusible condensation product whichconsists in combining approximately three parts of phenol with two partsof formaldehyde or one of its polymers by molecular weight and heatingthe same to form a fusible phenol resin, lncorporating therewithhexamethylene-tetra amin sufiicient in quantity to combine on heattreatment with all of the resin, andheating the mass sufficiently toform said hard infusible product, substantially as described.

10. The process of forming a hard infusible condensation product whichconsists in combining approximately three parts of phenol with two partsof formaldehyde or one of its polymers by molecular weight. heating thesame to form a fusible phenol resin, incorporating therewith from sevento twelve parts of heXa-methylene-tetraamin, and heating the masssufficiently to form said hard infusible product, substantially asdescribed.

11. As a new composition of matter, the

hard infusible product formed by the combination under suflicient heatof a fusible phenolic condensation product withhexamethylene-tetra-amin, substantially as described.

12. As a new composition of matter, the hard infusible product formed bythe combinationunder suflicient heat of an anhydrous fusible phenoliccondensation product with an anhydrous condensation productofformaldehyde or polymer thereof and ammonia, substantially as described.

13. As a new composition of matter, the hard infusible product formed bythe combination under suflicient heat of a fusible anhydrous phenoliccondensation product with anhydrous hexa-methylenetetra-amin,substantially as described.

This specification signed and witnessed this 8th day of February 1910.

JONAS W. AYLSWORTH.

Witnesses:

DYEJR SMITH, JOHN M. CANFmLD.

